3, 4-dichlorobenzyl nu-methylcarbamate herbicide



United States Patent Olfice 3,399,228 Patented Aug. 27, 1968 3,399,228 3,4-DICHLOROBENZYL N-METHYLCARBAMATE HERBICIDE Richard Herrett, Raleigh, N.C., and Robert V. Berthold,

South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Continuation-impart of application Ser. No. 269,874, Apr. 2, 1963. This application Sept. 15, 1965, Ser. No. 487,570

1 Claim. (Cl. 260-482) ABSTRACT OF THE DISCLOSURE 3,4-dichlorobenzyl N-methylcarbamate is usable as a contact herbicide and as a selective pre-emergence herbicide to control both broad leaf and grassy weeds.

This application is a continuation-in-part of Serial No. 269,874, filed Apr. 2, 1963, and now abandoned.

This invention relates to a new chemical compound useful as a contact herbicide when applied to plant foliage and as a selective herbicide when applied in pre-emergence treatment.

The undesirability of a mixed population of weed plants and crop plants is universally acknowledged. Weeds compete for sunlight, moisture, and nutrients; they harbour insects and disease; and they create serious problems in the harvest operation. The overall effect of weeds is a reduction in the crop value.

Efforts to combat these weed problems have been helped considerably by the introduction of chemicals possessing powerful hormonal properties. Generally, the chemicals will effectively remove broad-leaf weeds from narrow-leaf or grassy crops. These chemicals are not without problems, however. Because of their toxicity to broad-leaf plants, they will kill crops not of the narrowleaf class when accidentally sprayed on such crops. T-his danger can be substantially obviated by use of a selective pre-emergence herbicide. A second major disadvantage associated with these materials is their failure to control grassy weeds. This disadvantage has been alleviated to some extent with the introduction of new herbicides. Many new materials such as the triazines and substituted ureas are confronted with the problems of excessive soil residues and their uses are somewhat limited.

Heretofore, some of the most efficient and widely used selective pre-emergence herbicides were the N-aryl-O- alkyl carbamates, as exemplified by the commercially available isopropyl N-(3-chlorophenyl)carbamate. These chemicals, while very useful, possess inherent disadvantages that limit their application. For example, when applying isopropyl N-(3-chlorophenyl)carbamate there is often found a narrow margin of safety with respect to crop tolerance to the chemical, i.e., doses only slightly higher than those required for elfective weed control induce undesirable phytotoxic effects in the crop. In addition, the effectiveness of this chemical is highly sensitive to soil temperature (high activity is associated with low temperatures) and this sensitivity, coupled with the low degree of crop tolerance, frequently makes the use of this compound very hazardous. Another drawback to the use of these known carbamate herbicides resides in their highly variable residual life in the soil, again apparently influenced by temperature.

We have now found that a new compound possesses the basic desiderata of pro-emergence herbicides to a greater extent than do known materials and close structural relatives of our new compound. The compound of this invention is surprisingly superior in two fundamental respects:

(l) A high tolerance of the crop to our chemical is found at concentrations sufiicient for substantially com plete weed control, i.e. there is a broad margin of safety to avoid undesirable phytotoxic effects to the crop; and

(2) Broad-spectrum activity is displayed by our chemical with respect to variety of weed species controlled and this activity is coupled with broad-spectrum crop tolerance.

In addition, the compound of this invention possesses important secondary advantages in that its effectiveness is not highly susceptible to variation with changing environmental conditions. Thus, our material is effective at both low and relatively high soil temperatures, e. g. C., and its residual life appears not as adversely affected by ambient temperature changes as that of known materials.

Our material is 3,4-dichlorobenzyl N-methylcarbamate and can be depicted by the general formula:

We have found that the position of the halogen radicals on the phenyl ring has a profound influence on the herbicidal activity and selective action of the compound. Thus, substitution at both of the 3 and 4 positions is essential as demonstrated by the data in Table I, below, wherein several isomeric dichlorobenzyl N-methylcarbamates and some mono-chloro materials were evaluated.

We have further found that other structural character istics of our novel compounds are narrowly critical in that even minor variation thereof results in substantial loss of herbicidal activity. For example, if the carbamate nitrogen substitution is changed from N-methyl drastic reduction of bioactivity is observed (see Table II, below).

In addition, it has been demonstrated that alteration of the simple -CH linkage between the phenyl ring and the ether oxygen results in diminished effectiveness.

Our compound possesses activity both as pre-emergence and post-emergence herbicides and, accordingly, one aspect of this invention comprises the application of the material to undesired vegetation by any means whereby the material is brought into contact with living plants (which include seeds and germinating seedlings), e.g., by application to the soil before any plants emerge or by direct application to foliage.

While our material can be applied directly to nudesired vegetation and thus be used as an indiscriminate plant killer, we have found surprising selectivity when applying it to the soil in pre-emergence treatment. In such treatment both grassy weeds such as crabgrass, wild oats, barnyard grass, yellow foxtail, green foxtail, quack grass, and ryegrass, and broad-leaf weeds such as mustard, pigweed, lambs-quarters, and sheep sorrel are readily controlled while a broad spectrum of crops is unaffected. Illustrative of tolerant crops are cotton, soybeans, peanuts, beans, peas, onions, alfalfa, red clover, lespedeza,

field corn, and the like.

In addition to soil applications, our material is effective as an algaecide when applied to the media (e.g., water or soil) supporting the growth of algae.

Our new toxicant may be applied conveniently in the form of a spray containing the active ingredient in a concentration within the range of O.0120.0% by weight, and preferably from 1 to 10.0% by weight. Thorough coverage of the foliage is effective for contact killing. For preemergence control of plants amounts within the range of A to pounds per acre are generally used.

Although the ester is insoluble in Water, it is soluble in common organic solvents such as in acetone, chloroform, ethyl alcohol, ethyl acetate, benzene, ether and heptane.

The ester may be dispersed directly in water or a solution in an organic solvent emulsified in aqueous medium by the aid of a dispersing agent. As dispersing and wetting agents there may be employed soft or hard sodium or potassium soaps, alkylated aromatic sodium sulfonates such as sodium dodecylbenzenesulfonate, an amine salt as for example dibutylammonium dodecylbenzenesulfonate, alkali metal salts of sulfated fatty alcohols, ethylene oxide condensation products of alkyl phenols, or tall oil or higher mercaptans and other dispersing and wetting agents. Formulation of dry compositions is accomplished by mixing with finely divided solid carriers. Suitable carriers comprise talc, clay, pyrophyllite, silica and fullers earth. Usually the toxicant will be only a minor proportion. The dry formulation may be used as a dust or dispersed in aqueous medium before application. If the latter, it is convenient to incorporate a wetting or dispersing aid into the formuation.

Both the solid and the liquid formulations above described are useful in the application of herbicides because they facilitate uniform distribution and aid in the destruction of undesirable plants by maintaining the active ingredient in a form which enables prompt assimilation by the plant and efiicient utilization of its weed destroying properties. The described conditioning agents enable the proper use by an unskilled operator without elaborate equipment to achieve the desired herbicidal effects.

The compound of this invention is prepared by various techniques, analogous to known methods. One synthesis involves reacting a suitably substituted benzyl alcohol II ClQ-CHzOH with methyl isocyanate, O=O=NCH to give the desired N-methylcarbamate.

The methyl isocyanate addition can be carried out, generally, by contacting the alcohol with methyl isocyanate in an inert organic solvent, and preferably in the pres ence of a tertiary amine or organotin catalyst. The reaction may be effected at temperatures ranging from about C. to about 100 C., and is preferably carried out between room temperature and about 80 C. Generally, temperatures in excess of about 100 C. are to be avoided in view of the competing side reactions of the product carbamate. The operating pressure may range from about 1 atmosphere to about 10 atmospheres, preferably from about 2 to about 3 atmospheres, and is dependent upon the concentration and vapor pressure of the volatile isocyanate at the reaction temperature. The inert organic solvents that can be employed in the reaction are those inert to isocyanates in general, i.e. those free of radicals such as hydroxy or amino radicals. Illustrative solvents are aliphatic and aromatic hydrocarbons, such as hexane, heptane, octane, benzene, toluene, and the like, and ethers such as diethyl ether, ethyl propyl ether, and the like. The reaction is preferably carried out in the presence of a tertiary amine or an organotin catalyst or a combination thereof. Illustrative of tertiary amines suitable as catalysts are: N,N-dimethyl hydroxyethylamine, triethylene diamine, and dimethyl cyclohexylamine. The term organotin catalyst as used herein is meant to refer to such compounds as dibutyltin diacetate, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin dilaurate, dbutyltin maleate, dibutyltin di-Z-ethylhexenoate, stannous octanoate, stannous oleate, and the like. Generally, amounts of said catalyst from about 0.1 to 1.0 weight percent of the starting material comprised of methyl isocyanate and the benzyl alcohol are sufiicient. The mol ratio of methyl isocyanate to alcohol can range from 0.25:1 to about 4:1, but preferably an equimolar amount or slight excess of methyl isocyanate is employed to insure that the alcohol is completely reacted. The reaction time may vary from about 5 minutes to about 7 days, but normally, when operating in the preferred temperature range, reaction times of from about one-half hour to about five hours are sufficient for complete reaction.

The carbamate product formed can be recovered from the reaction mixture by means known to the art, e.g., by vacuum-distillation to drive off solvent and excess isocyanate.

An alternative procedure involves a two-step synthesis in which the alcohol (II) is reacted with phosgene to form the corresponding chloroformate which, in turn, is reacted with methylamine to give the desired compound as follows The chloroformate (III) is prepared by adding the alcohol (II) dissolved in an inert solvent, such as hydro carbon or ether, to a solution of phosgene, dissolved in the same solvent, at a temperature of 0 to 10 C. After allowing the reaction to come to completion by stirring for a period of 0.5 to 4 hours, the excess phosgene is removed under vacuum and the chloroformate stripped free of solvent and distilled. Alternatively, the chloroformate is used in the production of the carbamate as a residue product still contained in the reaction solvent.

The chloroformate is added to a percent excess of methylamine contained in a solvent of the type used in the preparation of the chloroformate. The amine is used in excess to remove the hydrogen chloride evolved during the reaction which is conducted below 30 C. After allowing the reaction to come to completion, which usually requires from 0.5 to 2 hours, the mixture is diluted with water, the layers are separated and the organic layer is washed with water and then dried over a suitable desiccant such as anhydrous sodium sulfate. The dried organic layer is distilled to remove the solvent and the resulting product carbamate, while usually sufiiciently pure to be used as a residue product, may be further purified by vacuum distillation or recrystallization from a suitable solvent.

The starting alcohol (II) is well known to the art and can be prepared by hydrolyzing the corresponding benzyl chlorides, or can be prepared by reducing the corresponding benzaldehyde or benzoic acid with, e.g., sodium borohydride or lithium aluminum hydride.

The following examples are illustrative.

EXAMPLE I 3,4-dichlorobenzyl alcohol was produced as follows: To a solution of 58 grams of 3,4-dichlorobenzaldehyde in 250 milliliters of methyl alcohol was added, with stirring, 9 grams of sodium borohydride in small portions and with occasional cooling to maintain the reaction temperature below 30 C. After the addition was completed, the reaction mixture was warmed to reflux, then cooled and diluted with water. The resulting mixture was extracted with portions of diethyl ether, the ether extracts were combined and dried over sodium sulfate. The ether was then. evaporated from the combined extracts and the residual oil was distilled through an eight-inch column to obtain a clear oily distillate product, boiling point 97 C. at 0.4 mm. Hg,

which solidified on cooling. The-yield of 3,4-dichlorobenzyl alcohol was 92 percent of the theoretical.

In accordance with the general procedure described above, a mixture of 20 grams of 3,4-dich1orobenzyl alcohol and 20 grams of methyl isocyanate in 50 milliliters of dry diethyl ether and one drop of dibutyltin diacetate was allowedto stand in a pressure bottle at room temperature for 48 hours. The ether and excess methyl isocyanate were then removed from the reaction mixture by distillation and the residual oil was distilled through an eight-inch Vigreux column to yield 3,4-dichlorobenzyl N-methylcarbamate as a colorless liquid distillate (boiling point 139 C. at 0.5 mm. Hg) which solidified upon cooling, melting point 534 C. The yield was 83 percent of the theoretical.

Elemental analysis. Calculated for C H NO Cl C=46.l8; H=3.87; N=5.98; Cl=30.29. Found: C: 46.35; H=3.80; N=6.10; Cl 30.03.

EXAMPLES II-VI Using exactly the same procedure as described for the preparation of 3,4 dichlorobenzyl N-methylcarbamate (Example I), employing one drop of dibutyltin diacetate as the catalyst in all cases, the following phenyl ring-substituted benzyl N-methylcarbamatcs were prepared in order to compare their herbicidal activity with that of the compound of this invention.

1 Boiling point, CJmm. Hg.

The effectiveness of our compound as a herbicide was determined by the following tests.

Suspensions of the test compound were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying o1- dispersing agent. The resulting solution or suspension was mixed into 150 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. The thus-prepared stock suspension contained 0.5 percent by weight of compound. The test concentrations employed in the tests described hereinbelow were obtained by diluting the stock suspension with water.

EXAMPLE V The compound of this invention was tested with regard to pre-emergence herbicidal activity, i.e., its ability to inhibit seed germination, or to kill the seedlings at an early stage of growth, by the following test.

Two seed-soil mixtures were prepared, the first by mixing 53 cubic centimeters of perennial ryegrass seed (Lolium perenne) and 27 cubic centimeters of Florida broadleaf mustard seed (Brassica pincea var. foliosa) with 6100 cubic centimeters of sifted, fairly dry soil, the second by mixing 31 cubic centimeters of golden millet seeds (Setaria italica var. stramineofructa) and 12 cubic centimeters of rcdroot seeds (Amaranthus retroflexus) with 6100 cubic centimeters of sifted, fairly dry soil. Each of the said two mixtures was rolled separately on a ball mill for about onehalf hour to insure uniform mixing of seed and soil, and, for each chemical to be tested, a three-inch pot was filled with each of the mixtures, and the pots removed to the greenhouse and watered lightly.

About two hours after such planting, 25 milliliters of test solution obtained by diluting the afore-described stock suspension to 1000 parts per million with water was added to each of two pots containing the two separate mixtures. A control test, carried out as above but without addition of test compound, was also performed. The pots were held in the greenhouse and watered lightly for three weeks at which time observations were made as to the extent of injury of each plant species and each test compound was rated according to the following designations.

5=no seedlings emerged, or those which did emerge subsequently died 4=few seedlings emerged, and many of those which did emerge subsequently died 3 =moderate reduction in stand 2=slight reduction in stand l=-no injury; seedlings appear no different with respect to stand or growth than control The results of these tests are set forth in Tables I and II below.

Q-orn- 3 4 2 a o1--om s 5 5 5 l Cl Thus it can be seen that of these five isomeric dichlorobenzyl compounds, the 3,4-dichlorobenzyl N-methylcarbamate is surprisingly outstanding in that complete kill of all four representative weed species was achieved.

Also tested according to the above procedure were the Since no phytotoxic response was induced by the monochloro materials even at the higher rate of four pounds TABLE II c1 per acre, additional tests were conducted to find the mini- Rl mum dosage required to cause substantial herbicidal ef- Scvd p y rating fects. This dosage was found to be sixteen pounds per acre Rye Millet Red- Musfor 4-chlorobenzyl N-methylcarbamate, but even at this ma rate, 4-chlorobenzyl N,N-dirnethylcarbamate caused no i= i damage to the weeds. 11 H 3 3 4 3 In order to compare the dichloro material with 4-chlorobenzyl-N-methylcarbamate with respect to h totoxicity CH3 p y in crop plants, a second series of tests was carried out 11 C11 1 2 2 1 using the above method but employing two varieties of CH3 lima beans and cotton as representative cro plants and e I p CH3 CH3 2 2 1 1 15 using a dosage at which. the monochloro material controls 1 1 1 1 weeds. The results are set forth in Table IV, below.

TABLE IV Rate Phytotoxicity Percent germination Chemical (lb./A.)

A B 0 A B o 3,4-dichlorobenzyl N-methylcarbamate.. 16 2. 2 2. 0 1. 3 83 80 100 4-chl0r0benzyl N -methylcarbaniate 16 3. 9 4. 7 3. 0 23 10 98 Control 1. 0 1. 0 1. 0 94 75 100 A=Henderson Lima Beans; B=Baby Fordhook Lima Beans; C=Coker 100A Cotton.

To explore more fully the pre-emergence herbicidal activity of our compound, in relation to two structural relatives which showed some activity at the massive concentration levels used in primary screening, the following serial dilution experiments were carried out.

Initially, all three compounds were tested against twenty representative weed species. The weed seeds were planted in 4-inch clay pots and, after planting, the chemicals were applied by watering the pots with milliliters of a standard water/acetone/emulsifier solution containing the chemical to give dosages corresponding to one pound per acre or four pounds per acre at a gallonage of about 6000 gallons per acre. After application of the chemicals, the pots were placed in the greenhouse and top watered. Phytoxicity observations were made 14 days after treatment and are expressed as ratings on a scale from 1 (no Stunting and burning of the leaves were noted when applying 4-chlorobenzyl N-met-hylcarbamate whereas only slight chlorosis around the midvein was observed in plants treated with 3,4-dichlorobenzyl N-methylcarbamate.

The effectiveness of 3,4-dichlorobenzyl N-methylcarbamate under actual field conditions is illustrated by the following test carried out under normal field conditions in the Southeastern United States.

A field was rototilled and row-seeded with the indicated crops and weeds in October. Immedicately thereafter, one-half liter portions of a test formulation, prepared by dissolving sufficient compound in equal volumes of water and acetone to give the indicated rates in pounds of compound per acre, were applied to the test plots which measured 3 feet by 10 feet (one plot for each plant species). Application of the formulation was made using elTect-equa1 to control) to 5 (complete kill). The rea hand sprayer having a single nozzle. Small amounts of suits are set forth in Table HI below. rain occurred twice between application and observation TABLE III 3,4-dichlorobenzyl, N-methylcar- 4-chlorobenzyl, N-methylcar- 4-chlorobenzyl, N ,N-dimethyl- Weed species 1 1b. bamate, 4 lb. 1 lb. bamate, 4 lb. 1 1b. CBI'bZIIIIlJMLC,

Perennial ryegrass 2 4 1 1 1 1 Crabgrass 2 5 1 1 1 1 Annual ryegi'ass 1 4 1 1 1 1 Yellow foxtail 3 5 1 1 1 1 Barnyard grass. 3 5 1 1 1 1 Tall millet 1 2 1 1 1 1 Pursland 2 5 1 1 1 1 Lamb's-qu 1 5 1 1 1 l Pigweed.-- 1 4 1 1 1 1 Wild oats- 1 3 1 1 1 1 Mustard. 1 2 1 1 1 1 Dallis grass" 1 5 1 1 l 1 Wild carrot" 1 2 1 1 1 1 Sheep sorrel 1 3 1 1 1 1 Buckthorn plantaim. 3 5 1 1 1 1 Morning glory 1 1 1 1 1 1 Quack grass. 1 4 1 1 1 1 Bromegrass. 1 1 1 1 1 1 Green fnxtail 2 4 1 1 1 1 Red brome. 1 3 1 1 1 1 9 10 of results. Eighteen days after application of the chemical sisted through the winter and good control of the carpet results were observed by visual inspection and the perweed (the only winter annual of the weeds used) was being formance of the compound against each plant species was maintained. rated according to the designations used above. The results Apart from the distinctive herbicidal activity of our are set forth in Table V, below. compound as herein disclosed, it also possesses utility as 5 an insecticide, fungicide, and bactericide. In addition, our

TABLE V.FIELD TEgT EVALUATION OF 3,4-DICHLOROBI%VNZ(;ZL N-METHYLOARBAMATE rops ee 5 Concentration (pounds per acre) Cotton Corn Mustard Ryegrass Green Crabgrass Carpet Quack ioxtail weed l grass I In this test the plot was naturally infested, not row-seeded, with carpet weed.

Further observation was made of the test plots during compound may be used to enhance or stimulate the the following spring and it was noted that the residual acgrowth of plants by using low concentrations, or othertion of 3,4dichlorobenzy1 N-methylcarbamate had perwise to modify plant growth.

What is claimed is: 1. 3,4-dichlorobenzy1N-methylcarbamate.

References Cited UNITED STATES PATENTS 2,776,197 1/1957 Gysin et a1 260-479 XR 2,933,383 4/1960 Lambrech 260-479 XR 2,992,091 7/ 1961 Harman et al. 260-455 XR 3,098,001 7/1963 Werres et a1. 260-482 XR 3,284,482 11/1966 DAmico et a1. 260-455 3,328,154 6/1967 DAmico 260-482 XR LORRAINE A. WEINBERGER, Primary Examiner.

A. P. HALLUIN, Assistant Examiner. 

